Oxidative Synthesis of Bioactive B‐3 Analogue of Procyanidin with 3,4‐cis Stereochemistry

Abstract

AbstractProcyanidins are polyphenols naturally ubiquitous in fruits, grains, seeds, nuts, plant barks and vegetables. However, isolating the natural bioactive compounds from plant materials produces mixtures of proanthocyanidins that are difficult to separate, thus compromising the yield of the desired pure–form procyanidins. Therefore, there is a need to synthesise high–yield homogeneous procyanidin compounds with well‐defined stereo‐ and regiochemistry. This study describes a method for synthesising the free phenolic procyanidin B‐3 analogue. Treatment of a solution of tetra‐O‐benzyl‐3‐oxocatechin 3 b (1 equiv.) and penta‐O‐benzylcatechin 2 c (3 equiv.) with silver tetrafluoroborate (AgBF4) readily afford the per‐O‐benzyl ethers of 3‐oxo‐catechin‐(4→8)‐catechin 18 exclusively. Subsequent sodium borohydride reduction followed by catalytic hydrogenation afforded the free phenolic B‐3 procyanidin (catechin‐(4β→8)‐catechin) 20 with 3,4‐cis Stereochemistry in a good percentage yield of 86 %.